Activating a high-spin iron(II) complex to thermal spin-crossover with an inert non-isomorphous molecular dopant.

[Fe(bpp)2][ClO4]2 (bpp = 2,6-bis{pyrazol-1-yl}pyridine; monoclinic, C2/c) is high-spin between 5-300 K, and crystallises with a highly distorted molecular geometry that lies along the octahedral-trigonal prismatic distortion pathway. In contrast, [Ni(bpp)2][ClO4]2 (monoclinic, P21) adopts a more regular, near-octahedral coordination geometry. Gas phase DFT minimisations (ω-B97X-D/6-311G**) of [M(bpp)2]2+ complexes show the energy penalty associated with that coordination geometry distortion runs as M2+ = Fe2+ (HS) ≈ Mn2+ (HS) < Zn2+ ≈ Co2+ (HS) ≲ Cu2+ ≪ Ni2+ ≪ Ru2+ (LS; HS = high-spin, LS = low-spin). Slowly crystallised solid solutions [FexNi1-x(bpp)2][ClO4]2 with x = 0.53 (1a) and 0.74 (2a) adopt the P21 lattice, while x = 0.87 (3a) and 0.94 (4a) are mixed-phase materials with the high-spin C2/c phase as the major component. These materials exhibit thermal spin-transitions at T½ = 250 ± 1 K which occurs gradually in 1a, and abruptly and with narrow thermal hysteresis in 2a-4a. The transition proceeds to 100% completeness in 1a and 2a; that is, the 26% Ni doping in 2a is enough to convert high-spin [Fe(bpp)2][ClO4]2 into a cooperative, fully SCO-active material. These results were confirmed crystallographically for 1a and 2a, which revealed similarities and differences between these materials and the previously published [FexNi1-x(bpp)2][BF4]2 series. Rapidly precipitated powders with the same compositions (1b-4b) mostly resemble 1a-4a, except that 2b is a mixed-phase material; 2b-4b also contain a fraction of amorphous solid in addition to the two crystal phases. The largest iron fraction that can be accommodated by the P21 phase in this system is 0.7 ± 0.1.

Electrothermal Transformations within Graphene-Based Aerogels through High-Temperature Flash Joule Heating.

Flash Joule heating of highly porous graphene oxide (GO) aerogel monoliths to ultrahigh temperatures is exploited as a low carbon footprint technology to engineer functional aerogel materials. Aerogel Joule heating to up to 3000 K is demonstrated for the first time, with fast heating kinetics (∼300 K·min-1), enabling rapid and energy-efficient flash heating treatments. The wide applicability of ultrahigh-temperature flash Joule heating is exploited in a range of material fabrication challenges. Ultrahigh-temperature Joule heating is used for rapid graphitic annealing of hydrothermal GO aerogels at fast time scales (30-300 s) and substantially reduced energy costs. Flash aerogel heating to ultrahigh temperatures is exploited for the in situ synthesis of ultrafine nanoparticles (Pt, Cu, and MoO2) embedded within the hybrid aerogel structure. The shockwave heating approach enables high through-volume uniformity of the formed nanoparticles, while nanoparticle size can be readily tuned through controlling Joule-heating durations between 1 and 10 s. As such, the ultrahigh-temperature Joule-heating approach introduced here has important implications for a wide variety of applications for graphene-based aerogels, including 3D thermoelectric materials, extreme temperature sensors, and aerogel catalysts in flow (electro)chemistry.

Universality of Hair as a Nucleant: Exploring the Effects of Surface Chemistry and Topography.

The ability to control crystal nucleation through the simple addition of a nucleating agent (nucleant) is desirable for a huge range of applications. However, effective nucleating agents are known for only a small number of systems, and many questions remain about the mechanisms by which they operate. Here, we explore the features that make an effective nucleant and demonstrate that the biological material hair-which naturally possesses a chemically and topographically complex surface structure-has excellent potential as an effective nucleating agent. Crystallization of poorly soluble compounds in the presence of hairs from a range of mammals shows that nucleation preferentially occurs at the cuticle step edges, while a novel microdroplet-based methodology was used to quantify the nucleating activities of different hairs. This showed that the activities of the hairs can be tuned over a wide range using chemical treatments. Analysis of the hair structure and composition using atomic force microscopy, scanning ion conductance microscopy, and X-ray photoelectron spectroscopy demonstrates that surface chemistry, surface topography, and surface charge all act in combination to create effective nucleation sites. This work therefore contributes to our understanding of heterogeneous nucleating agents and shows that surface topography as well as surface chemistry can be used in the design or selection of universal nucleating agents.

Polyamines Promote Aragonite Nucleation and Generate Biomimetic Structures.

Calcium carbonate biomineralization is remarkable for the ability of organisms to produce calcite or aragonite with perfect fidelity, where this is commonly attributed to specific anionic biomacromolecules. However, it is proven difficult to mimic this behavior using synthetic or biogenic anionic organic molecules. Here, it is shown that cationic polyamines ranging from small molecules to large polyelectrolytes can exert exceptional control over calcium carbonate polymorph, promoting aragonite nucleation at extremely low concentrations but suppressing its growth at high concentrations, such that calcite or vaterite form. The aragonite crystals form via particle assembly, giving nanoparticulate structures analogous to biogenic aragonite, and subsequent growth yields stacked aragonite platelets comparable to structures seen in developing nacre. This mechanism of polymorph selectivity is captured in a theoretical model based on these competing nucleation and growth effects and is completely distinct from the activity of magnesium ions, which generate aragonite by inhibiting calcite. Profiting from these contrasting mechanisms, it is then demonstrated that polyamines and magnesium ions can be combined to give unprecedented control over aragonite formation. These results give insight into calcite/aragonite polymorphism and raise the possibility that organisms may exploit both amine-rich organic molecules and magnesium ions in controlling calcium carbonate polymorph.

Serial small- and wide-angle X-ray scattering with laboratory sources.

Recent advances in X-ray instrumentation and sample injection systems have enabled serial crystallography of protein nanocrystals and the rapid structural analysis of dynamic processes. However, this progress has been restricted to large-scale X-ray free-electron laser (XFEL) and synchrotron facilities, which are often oversubscribed and have long waiting times. Here, we explore the potential of state-of-the-art laboratory X-ray systems to perform comparable analyses when coupled to micro- and millifluidic sample environments. Our results demonstrate that commercial small- and wide-angle X-ray scattering (SAXS/WAXS) instruments and X-ray diffractometers are ready to access samples and timescales (≳5 ms) relevant to many processes in materials science including the preparation of pharmaceuticals, nanoparticles and functional crystalline materials. Tests of different X-ray instruments highlighted the importance of the optical configuration and revealed that serial WAXS/XRD analysis of the investigated samples was only possible with the higher flux of a microfocus setup. We expect that these results will also stimulate similar developments for structural biology.

Positively Charged Additives Facilitate Incorporation in Inorganic Single Crystals.

Incorporation of guest additives within inorganic single crystals offers a unique strategy for creating nanocomposites with tailored properties. While anionic additives have been widely used to control the properties of crystals, their effective incorporation remains a key challenge. Here, we show that cationic additives are an excellent alternative for the synthesis of nanocomposites, where they are shown to deliver exceptional levels of incorporation of up to 70 wt % of positively charged amino acids, polymer particles, gold nanoparticles, and silver nanoclusters within inorganic single crystals. This high additive loading endows the nanocomposites with new functional properties, including plasmon coupling, bright fluorescence, and surface-enhanced Raman scattering (SERS). Cationic additives are also shown to outperform their acidic counterparts, where they are highly active in a wider range of crystal systems, owing to their outstanding colloidal stability in the crystallization media and strong affinity for the crystal surfaces. This work demonstrates that although often overlooked, cationic additives can make valuable crystallization additives to create composite materials with tailored composition-structure-property relationships. This versatile and straightforward approach advances the field of single-crystal composites and provides exciting prospects for the design and fabrication of new hybrid materials with tunable functional properties.

Incorporation of nanogels within calcite single crystals for the storage, protection and controlled release of active compounds.

Nanocarriers have tremendous potential for the encapsulation, storage and delivery of active compounds. However, current formulations often employ open structures that achieve efficient loading of active agents, but that suffer undesired leakage and instability of the payloads over time. Here, a straightforward strategy that overcomes these issues is presented, in which protein nanogels are encapsulated within single crystals of calcite (CaCO3). Demonstrating our approach with bovine serum albumin (BSA) nanogels loaded with (bio)active compounds, including doxorubicin (a chemotherapeutic drug) and lysozyme (an antibacterial enzyme), we show that these nanogels can be occluded within calcite host crystals at levels of up to 45 vol%. Encapsulated within the dense mineral, the active compounds are stable against harsh conditions such as high temperature and pH, and controlled release can be triggered by a simple reduction of the pH. Comparisons with analogous systems - amorphous calcium carbonate, mesoporous vaterite (CaCO3) polycrystals, and calcite crystals containing polymer vesicles - demonstrate the superior encapsulation performance of the nanogel/calcite system. This opens the door to encapsulating a broad range of existing nanocarrier systems within single crystal hosts for the efficient storage, transport and controlled release of various active guest species.

Facile Synthesis of Electrically Conductive and Heatable Nanoparticle/Nanocarbon Hybrid Aerogels.

Joule heating studies on nanoparticle/nanocarbon hybrid aerogels have been reported, but systematic investigations on hydrotalcite-derived catalysts supported onto reduced graphene oxide (rGO) aerogels are rare. In this study, hydrotalcite-derived Cu-Al2O3 nanoparticles were incorporated into a porous and multifunctional rGO aerogel support for fabricating electrically conducting Cu-Al2O3/rGO hybrid aerogels, and their properties were investigated in detail. The hybridization of Cu-Al2O3 with a 3D nanocarbon support network imparts additional functionalities to the widely used functional inorganic nanoparticles, such as direct electrical framework heating and easy regeneration and separation of spent nanoparticles, with well-spaced nanoparticle segregation. 3D variable-range hopping model fitting confirmed that electrons were able to reach the entire aerogel to enable uniform resistive heating. The conductivity of the nanocarbon support framework facilitates uniform and fast heating (up to 636 K/min) of the embedded nanoparticles at very low energy consumption, while the large porosity and high thermal conductivity enable efficient heat dissipation during natural cooling (up to 336 K/min). The thermal stability of the hybrid aerogel was demonstrated by repeated heating/cooling cycling at different temperatures that were relevant to important industrial applications. The facile synthetic approach can be easily adapted to fabricate other types of multifunctional nanoparticle/nanocarbon hybrid aerogels, such as the MgAl-MMO/rGO aerogel and the Ni-Al2O3/rGO aerogel. These findings open up new routes to the functionalization of inorganic nanoparticles and extend their application ranges that involve electrical/thermal heating, temperature-dependent catalysis, sorption, and sensing.

Pyrene Tags for the Detection of Carbohydrates by Label-Assisted Laser Desorption/Ionisation Mass Spectrometry*.

Matrix-assisted laser desorption/ionisation mass spectrometry (MALDI-MS) is widely used for the analysis of biomolecules. Label-assisted laser desorption/ionisation mass spectrometry (LALDI-MS) is a matrix-free variant of MALDI-MS, in which only analytes covalently attached to a laser desorption/ionisation (LDI) enhancer are detected. LALDI-MS has shown promise in overcoming the limitations of MALDI-MS in terms of sample preparation and MS analysis. In this work, we have developed a series of pyrene-based LDI reagents (LALDI tags) that can be used for labelling and LALDI-MS analysis of reducing carbohydrates from complex (biological) samples without the need for additional chemical derivatisation or purification. We have systematically explored the suitability of four pyrene-based LDI enhancers and three aldehyde-reactive handles, optimised sample preparation, and demonstrated the use of LALDI tags for the detection of lactose. We have also exemplified the potential of LALDI tags for labelling carbohydrates in biological samples by direct detection of lactose in cow's milk. These results demonstrate that LALDI-MS is a promising technique for the analysis of reducing carbohydrates in biological samples, and pave the way for the development of LALDI-MS for glycomics and diagnostics.

Ptychographic X-ray tomography reveals additive zoning in nanocomposite single crystals.

Single crystals containing nanoparticles represent a unique class of nanocomposites whose properties are defined by both their compositions and the structural organization of the dispersed phase in the crystalline host. Yet, there is still a poor understanding of the relationship between the synthesis conditions and the structures of these materials. Here ptychographic X-ray computed tomography is used to visualize the three-dimensional structures of two nanocomposite crystals - single crystals of calcite occluding diblock copolymer worms and vesicles. This provides unique information about the distribution of the copolymer nano-objects within entire, micron-sized crystals with nanometer spatial resolution and reveals how occlusion is governed by factors including the supersaturation and calcium concentration. Both nanocomposite crystals are seen to exhibit zoning effects that are governed by the solution composition and interactions of the additives with specific steps on the crystal surface. Additionally, the size and shape of the occluded vesicles varies according to their location within the crystal, and therefore the solution composition at the time of occlusion. This work contributes to our understanding of the factors that govern nanoparticle occlusion within crystalline materials, where this will ultimately inform the design of next generation nanocomposite materials with specific structure/property relationships.

Demonstration of Visible Light-Activated Photocatalytic Self-Cleaning by Thin Films of Perovskite Tantalum and Niobium Oxynitrides.

Metal oxynitrides adopting the perovskite structure have been shown to be visible light-activated photocatalysts, and therefore, they have potential as self-cleaning materials where surface organic pollutants can be removed by photomineralization. In this work, we establish a route for the deposition of thin films for seven perovskite oxynitrides, CaTaO2N, SrTaO2N, BaTaO2N, LaTaON2, EuTaO2N, SrNbO2N, and LaNbON2, on quartz and alumina substrates using dip-coating of a polymer gel to form an amorphous oxide precursor film, followed by ammonolysis. The initially deposited oxide films were annealed at 800 °C, followed by ammonolysis at temperatures from 850 to 1000 °C. The perovskite oxynitride thin films were characterized using XRD and EDX, with band gaps determined using Tauc plots derived from UV-vis spectroscopic data. A cobalt oxide co-catalyst was deposited onto each film by drop casting, and the photocatalytic activity assessed under visible light using dichloroindophenol dye degradation in the presence of a sacrificial oxidant. The light source used was a solar simulator equipped with a 400 nm cut-off filter. The dye degradation test demonstrated photocatalytic activity in all samples except EuTaO2N and BaTaO2N. The three most active samples were SrNbO2N, CaTaO2N, and SrTaO2N. The cobalt oxide loading was optimized for these three films and found to be 0.3 µg cm-2. Further, catalytic tests were conducted using stearic acid degradation, and this found the film of SrNbO2N with the cobalt oxide co-catalyst to be the most active for complete mineralization of this model pollutant.

Hydroxyl-rich macromolecules enable the bio-inspired synthesis of single crystal nanocomposites.

Acidic macromolecules are traditionally considered key to calcium carbonate biomineralisation and have long been first choice in the bio-inspired synthesis of crystalline materials. Here, we challenge this view and demonstrate that low-charge macromolecules can vastly outperform their acidic counterparts in the synthesis of nanocomposites. Using gold nanoparticles functionalised with low charge, hydroxyl-rich proteins and homopolymers as growth additives, we show that extremely high concentrations of nanoparticles can be incorporated within calcite single crystals, while maintaining the continuity of the lattice and the original rhombohedral morphologies of the crystals. The nanoparticles are perfectly dispersed within the host crystal and at high concentrations are so closely apposed that they exhibit plasmon coupling and induce an unexpected contraction of the crystal lattice. The versatility of this strategy is then demonstrated by extension to alternative host crystals. This simple and scalable occlusion approach opens the door to a novel class of single crystal nanocomposites.

Observation of visible light activated photocatalytic degradation of stearic acid on thin films of tantalum oxynitride synthesized by aerosol assisted chemical vapour deposition.

UV activated photocatalysts deposited using chemical vapour deposition have found commercial success as self-cleaning coatings. However, only limited work has been conducted on the use of the more recently discovered visible light activated photocatalysis for this application. Tantalum oxynitride is an established visible light photocatalyst, and in this paper we have investigated the ability of thin films of tantalum oxynitride to photocatalytically degrade a model organic pollutant, stearic acid, and therefore assess the coatings potential for self-cleaning applications. Thin films of tantalum oxide were formed using aerosol assisted chemical vapour deposition (AACVD) of tantalum ethoxide, and then converted into tantalum oxynitride through ammonolysis at temperatures between 550 °C and 750 °C. Investigation of the films using XRD, UV-vis spectroscopy and XAFS identify that amorphous tantalum oxynitride is formed during the ammonolysis, with complete conversion to TaON under conditions of 700 °C for 24 hours. The self-cleaning ability of this film was assessed using stearic acid as the model pollutant, with a degradation rate of 2.5(2) × 1013 molecules per min per cm2 when exposed to a 5-sun solar simulator, equipped with a UV cut-off filter. We therefore conclude that tantalum oxynitride thin films are able to act as self-cleaning coatings through visible light photocatalysis and that films of tantalum oxynitride can be synthesized using a scalable chemical vapour deposition route.

Spatially Controlled Occlusion of Polymer-Stabilized Gold Nanoparticles within ZnO.

In principle, incorporating nanoparticles into growing crystals offers an attractive and highly convenient route for the production of a wide range of novel nanocomposites. Herein we describe an efficient aqueous route that enables the spatially controlled occlusion of gold nanoparticles (AuNPs) within ZnO crystals at up to 20 % by mass. Depending on the precise synthesis protocol, these AuNPs can be (i) solely located within a central region, (ii) uniformly distributed throughout the ZnO host crystal or (iii) confined to a surface layer. Remarkably, such efficient occlusion is mediated by a non-ionic water-soluble polymer, poly(glycerol monomethacrylate)70 (G70 ), which is chemically grafted to the AuNPs; pendent cis-diol side groups on this steric stabilizer bind Zn2+ cations, which promotes nanoparticle interaction with the growing ZnO crystals. Finally, uniform occlusion of G70 -AuNPs within this inorganic host leads to faster UV-induced photodegradation of a model dye.

Generation of ultra-stable Pickering microbubbles via poly alkylcyanoacrylates.

A range of solution conditions (pH, surfactant concentration and type) have been tested for the polymerization of alkyl cyanoacrylates (ethyl (ECA), butyl (BCA) and octyl (OCA)) into nanoparticles (NPs) potentially capable of stabilizing highly unstable microbubbles (MBs) of air in aqueous solutions. The optimum system was butyl cyanoacrylate (BCA) polymerized into PBCA particles at pH 4 in the presence of 1 wt.% Tyloxapol surfactant. These PBCA particles were highly effective at stabilizing MBs of only a few microns in size for at least 2 months. Microscopy over a range of length scales clearly indicated that these particles were stabilized via a Pickering mechanism. Only a relatively low volume fraction (ca. 1 vol.%) of MBs could be obtained via a single aeration step of a 0.7 wt.% dispersion of PBCA particles in a high shear mixer. Although this could be increased to 2 and 3 vol.% by second and third aerations, this reflects the difficulty of obtaining and maintaining rapid enough particle coverage of small bubbles even under turbulent conditions. Similar sizes and yields of PBCA particles could be obtained in the absence of surfactants, but these particles, with or without addition of surfactant afterwards, could not stabilize MBs. We estimate that approximately one quarter of the Tyloxapol when present during polymerization is incorporated into the particles on polymerization, which somehow imparts the correct surface hydrophobicity and contact angle to the particles at the A/W interface, making such particles so very effective as Pickering MB stabilizers.

Anionic block copolymer vesicles act as Trojan horses to enable efficient occlusion of guest species into host calcite crystals.

We report a versatile 'Trojan Horse' strategy using highly anionic poly(methacrylic acid)-poly(benzyl methacrylate) vesicles to incorporate two types of model payloads, i.e. either silica nanoparticles or an organic dye (fluorescein), within CaCO3 (calcite). Uniform occlusion of silica-loaded vesicles was confirmed by scanning electron microscopy, while thermogravimetry studies indicated extents of vesicle occlusion of up to 9.4% by mass (∼33% by volume). Efficient dye-loaded vesicle occlusion produces highly fluorescent calcite crystals as judged by fluorescence microscopy. In control experiments, silica nanoparticles alone are barely occluded, while only very weakly fluorescent calcite crystals are obtained when using just the fluorescein dye. This new 'Trojan Horse' strategy opens up a generic route for the efficient occlusion of various nanoparticles and organic molecules within inorganic host crystals.

Phosphinecarboxamide as an unexpected phosphorus precursor in the chemical vapour deposition of zinc phosphide thin films.

This paper demonstrates the use of phosphinecarboxamide as a facile phosphorus precursor, which can be used alongside zinc acetate for the chemical vapour deposition (CVD) of adherent and crystalline zinc phosphide films. Thin films of Zn3P2 have a number of potential applications and phosphinecarboxamide is a safer and more efficient precursor than the highly toxic, corrosive and flammable phosphine used in previous CVD syntheses.

Combining single source chemical vapour deposition precursors to explore the phase space of titanium oxynitride thin films.

In this paper we report on a novel chemical vapour deposition approach to the formation and control of composition of mixed anion materials, as applied to titanium oxynitride thin films. The method used is the aerosol assisted chemical vapour deposition (AACVD) of a mixture of single source precursors. To explore the titanium-oxygen-nitrogen system the single source precursors selected were tetrakis(dimethylamido) titanium and titanium tetraisopropoxide which individually are precursors to thin films of titanium nitride and titanium dioxide respectively. However, by combining these precursors in specific ratios in a series of AACVD reactions at 400 °C, we are able to deposit thin films of titanium oxynitride with three different structure types and a wide range of compositions. Using this precursor system we can observe films of nitrogen doped anatase, with 25% anion doping of nitrogen; a new composition of pseudobrookite titanium oxynitride with a composition of Ti3O3.5N1.5, identified as being a UV photocatalyst; and rock-salt titanium oxynitride in the range TiO0.41N0.59 to TiO0.05N0.95. The films were characterised using GIXRD, WDX and UV-vis spectroscopy, and in the case of the pseudobrookite films, assessed for photocatalytic activity. This work shows that a so-called dual single-source CVD approach is an effective method for the deposition of ternary mixed anion ceramic films through simple control of the ratio of the precursors, while keeping all other experimental parameters constant.

Heterometallic Coordination Polymer Gels Supported by 2,4,6-Tris(pyrazol-1-yl)-1,3,5-triazine.

Complexes of type [M(tpt)2]X2 (M2+ = Fe2+, Co2+, Ni2+; tpt = 2,4,6-tri{pyrazol-1-yl}-1,3,5-triazine; X- = BF4 - or ClO4 -) crystallize in a cubic lattice, with the metal ion and ligand conformation showing unusual symmetry-imposed disorder. Addition of 1 equiv AgX to the corresponding preformed [M(tpt)2]X2 salt in concentrated MeNO2 solution affords thixotropic gels. Gelation was not observed in analogous reactions using [Mn(tpt)2][ClO4]2, or from reactions in other, more donating solvents. Scanning electron microscopy (SEM) images from dilute solutions of the reagents confirmed the fibrous microstructure of the gels and their homogeneous elemental composition. However, energy-dispersive X-ray data show a reduced Fe/Ag ratio compared to the Co/Ag and Ni/Ag gels, where a 1:1 ratio of metals is evident. More concentrated gels decomposed to silver nanoparticles during SEM sample preparation. Mass spectrometry and 1H NMR indicate that silver induces partial ligand displacement reactions in [Fe(tpt)2]2+ and [Co(tpt)2]2+, but not in [Ni(tpt)2]2+. Hence, the strength of the gels, which follows the order M = Mn (no gel) < Fe < Co < Ni, correlates with the stability of octahedral [M(tpt)2]2+ under gelation conditions. Iron(II) complexes of the related ligands 2,4,6-tri{pyrazol-1-yl}pyridine (tpp) and 2,4,6-tri{pyrazol-1-yl}pyrimidine (tpym) did not undergo gelation with silver salts under the above conditions. The unique properties of tpt as a gelator in this work may reflect the crystallographically observed ability of metal-coordinated tpt to chelate to exogenous silver ions, through its pendant pyrazolyl group and triazinyl N donors. In contrast, the pendant azolyl substituents in silver complexes of the nongelators tpp and tpym only bind exogenous silver in monodentate fashion.

The role of phase separation and related topography in the exceptional ice-nucleating ability of alkali feldspars.

Our understanding of crystal nucleation is a limiting factor in many fields, not least in the atmospheric sciences. It was recently found that feldspar, a component of airborne desert dust, plays a dominant role in triggering ice formation in clouds, but the origin of this effect was unclear. By investigating the structure/property relationships of a wide range of feldspars, we demonstrate that alkali feldspars with certain microtextures, related to phase separation into Na and K-rich regions, show exceptional ice-nucleating abilities in supercooled water. We found no correlation between ice-nucleating efficiency and the crystal structures or the chemical compositions of these active feldspars, which suggests that specific topographical features associated with these microtextures are key in the activity of these feldspars. That topography likely acts to promote ice nucleation, improves our understanding of ice formation in clouds, and may also enable the design and manufacture of bespoke nucleating materials for uses such as cloud seeding and cryopreservation.